Catalyst composition, method of polymerization and polymer therefrom

ABSTRACT

This invention relates to a process to polymerize olefin(s) comprising combining a solution, slurry or solid comprising one or more bulky ligand metallocene catalyst compounds, an optional support, and or one or more activator(s) with a solution comprising one or more phenoxide catalyst compounds, and thereafter, introducing one or more olefin(s) and the combination into a polymerization reactor. This invention also relates to a polymer of ethylene wherein the polymer has a density of 0.910 to 0.930 g/cc, a melt index of 0.3 to 2.0 dg/min, and a 15 to 35 μm thick film of the polymer has a 45° gloss of 60 or more, a haze of 7% or less, and a dart impact of 600 g or more.

STATEMENT OF RELATED APPLICATIONS

The present application is a Divisional Application of, and claimspriority to U.S. Ser. No. 09/729,557 filed Dec. 04, 2000, now issued asU.S. Pat. No. ______.

FIELD OF THE INVENTION

This invention is directed to a process for polymerizing olefin(s) wherea solution, slurry or solid comprising at least one bulky ligandmetallocene catalyst compound and at least one activator and a solutioncomprising at least one phenoxide catalyst compound are combined priorto being introduced to a polymerization reactor.

BACKGROUND OF THE INVENTION

Advances in polymerization and catalysis have resulted in the capabilityto produce many new polymers having improved physical and chemicalproperties useful in a wide variety of superior products andapplications. With the development of new catalysts the choice ofpolymerization (solution, slurry, high pressure or gas phase) forproducing a particular polymer has been greatly expanded. Also, advancesin polymerization technology have provided more efficient, highlyproductive and economically enhanced processes. Especially illustrativeof these advances is the development of technology utilizing bulkyligand metallocene catalyst systems. In a slurry or gas phase processtypically a supported catalyst system is used, however, more recentlyunsupported catalyst systems are being used in these processes. Forexample, U.S. Pat. Nos. 5,317,036 and 5,693,727 and European publicationEP-A-0 593 083 and PCT publication WO 97/46599 all describe variousprocesses and techniques for introducing liquid catalysts to a reactor.There is a desire in the industry using this technology to reduce thecomplexity of the process, to improve the process operability, toincrease product characteristics and to vary catalyst choices. Thus, itwould be advantageous to have a process that is capable of improving oneor more of these industry needs.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates an example of an equipment configuration for apreferred embodiment of the invention.

SUMMARY OF THE INVENTION

This invention is directed to a process for polymerizing olefin(s) wherea solution, slurry or a solid comprising a bulky ligand metallocenecatalyst compound and at least one activator (Component A) and asolution comprising at least one phenoxide catalyst compound (ComponentB) are combined, preferably in-line, prior to being introduced to apolymerization reactor. The length of time that Component A andComponent B are contacted in the mixer is typically up to about 120minutes, preferably about 1 to about 60 minutes, more preferably about 5to about 40 minutes, even more preferably about 10 to about 30 minutes.

This invention also relates to a polymer of ethylene wherein the polymerhas a density of 0.910 to 0.930 g/cc, a melt index of 0.3-2.0 dg/min,and a 15-35 Jim thick film of the polymer has a 45° gloss of 60 or more,a haze of 7% or less, a dart impact of 600 g or more and in a preferredembodiment the films also have:

-   -   a) a TD tensile strength of 30 MPa or more, and or    -   b) an MD tensile strength of 30 MPa or more, and or    -   b) an MD and or TD modulus of 150 or more and or    -   c) an MD Elmendorf tear of 180 g/mil or more, and or    -   d) a TD Elmendorf tear of 300 g/mil or more.

DETAILED DESCRIPTION OF THE INVENTION

For purposes of this invention and the claims thereto a catalyst systemcomprises at least one activator and at least one catalyst compound. Forthe purposes of this invention a slurry is defined to be a suspension ofa solid in a liquid. The solid may or may not be porous.

In a preferred embodiment both Component A and Component B areintroduced into the reactor in a solution or solutions. For moreinformation on methods to feed multiple solution catalysts into apolymerization reactor, please see U.S. Ser. No. 09//451,792, filed Dec.1, 1999 and incorporated by reference herein. In some embodiments, forexample, the catalyst system, the metal compounds and or the activatormay be introduced into the reactor in one or more solutions. In oneembodiment, a solution of the two activated metal compounds in an alkanesuch as pentane, hexane, toluene, isopentane or the like is introducedinto a gas phase or slurry phase reactor. In another embodiment thecatalysts system or the components can be introduced into the reactor ina suspension or an emulsion. In one embodiment, the second metalcompound is contacted with the activator, such as modifiedmethylalumoxane, in a solvent and just before the solution is fed into agas or slurry phase reactor. In another embodiment, a solution of thefirst metal compound is combined with a solution of the second compoundand the activator then introduced into the reactor. In a preferredembodiment, the solution is introduced into the reactor via a plenumwhich is described in U.S. Pat. No. 5,693,727, incorporated by referenceherein.)

In another embodiment, Component A is a slurry or a solid comprising asupport, a bulky ligand metallocene catalyst compound and at least oneactivator (supported Component A) and Component B is a solutioncomprising at least one phenoxide catalyst compound.

Typically, the bulky ligand metallocene catalyst compound(s) and thesupport are allowed to contact each other for a time sufficient for atleast 50% of the catalyst compounds to be deposited in or on thesupport, preferably at least 70%, preferably at least 80%, morepreferably at least 90%. Times allowed for mixing are up to 10 hours,typically up to 6 hours, more typically 4-6 hours. The bulky ligandmetallocene compounds may be combined with the support in a liquid, suchas mineral oil, toluene, hexane, etc. and may thereafter optionally bedried to a solid state, such as a powder.

After contacting supported Component A with Component B, all orsubstantially all, preferably at least 50% preferably at least 70%,preferably at least 75%, preferably at least 80%, more preferably atleast 90%, preferably at least 95%, preferably at least 99% of thecatalyst compound from the Component B is deposited in or on the supportinitially contained in the Component A. For purposes of this invention acatalyst compound will be considered to be in or on the support if theconcentration of the catalyst compound in the liquid portion of thecombination is reduced over time after adding the catalyst compound.Concentration of the catalyst compound may be measured for example, bygas chromatography (GC) mass spectroscopy (MS) after standardizationwith a calibration curve prepared at the appropriate concentration,range as is known in the art. Thus for example, 70% of a catalystcompound will be considered to have deposited in or on a support if theconcentration of the catalyst compound in the liquid (not including thesupport) is reduced by 70% from its initial concentration.

The Component B may comprise additional activator or catalyst compounds.In another preferred embodiment activator is not present in Component B.In a preferred embodiment activator is present in Component B at lessthan I weight %, preferably less than 1000 ppm, preferably less than 100ppm.

The support material may be any inert particulate carrier material knownin the art, including, but not limited to, silica, fumed silica,alumina, clay, talc or other materials as disclosed below. In apreferred embodiment the activator is placed upon the support first tofor supported activator and thereafter is contacted with the bulkyligand metallocene compound(s). A preferred supported activator isalumoxane and or modified alumoxane on silica or fumed silica,preferably methyl alumoxane and/or modified methyl alumoxane on asupport of fumed silica.

In a particularly preferred embodiment, alumoxane, preferably methylalumoxane or modified methyl alumoxane, is combined with a support suchas calcined silica or fumed silica to form a supported activator, thesupported activator is then dispersed in a liquid, such as degassedmineral oil to form a slurry, and then one or bulky ligand metallocenecompounds are added to the dispersion and mixed. The catalyst compoundsare preferably added to the dispersion as a powder or a solution,preferably a solution of mineral oil. If more than one catalyst compoundis added to the dispersion, the catalyst compounds can be addedsequentially or at the same time.

In a preferred embodiment the concentration of solids in supportedComponent A is maintained at greater than 0 to 90 wt % solids, morepreferably 1 to 50 wt %, more preferably 5 to 40 wt %, even morepreferably 10 to 30 wt %, based upon the weight of Component A. Inanother preferred embodiment the activator is present on the support atbetween about 0.5 to about 7 mmol/g, preferably about 2 to about 6mmol/g, more preferably between about 4 to about 5 mmol/g.

Thereafter a solution comprising a phenoxide catalyst compound(Component B) is combined with the slurry. In a preferred embodiment,phenoxide catalyst compound is present in the solution at up to about 20wt %, preferably a up to about 10 wt%, more preferably up to about 5wt%, more preferably at less than I wt%, more preferably between 100 ppmand I wt % based upon the weight of the solvent and the phenoxidecatalyst compound.

In another preferred embodiment the total amount of catalyst compoundpresent on the support, preferably a supported activator, is about 1 toabout 40 μmol/g, preferably about 10 to about 38 μmol/g, more preferably30-36 μmol/g.

In one embodiment the final mole ratio (i.e. after combination of thebulky ligand catalyst compound(s) and the phenoxide metal compound(s))of the metal of the catalyst compounds and the metal of the activator isin the range of from about 1000:1 to about 0.5:1 preferably from about300:1 to about 1:1 more preferably from about 150:1 to about 1: 1; forboranes, borates, aluminates, etc., the ratio is preferably about 1:1 toabout 10:1 and for alkyl aluminum compounds (such as diethylaluminumchloride combined with water) the ratio is preferably about 0.5:1 toabout 10:1.

In a preferred embodiment supported Component A comprises mineral oiland has a viscosity of about 130 to about 2000 cP at 20° C., morepreferably about 150 to about 1000 cP at 20° C., more preferably about180 to about 1500 cP at 20° C. even more preferably about 200 to about800 cP at 20° C. as measured with a Brookfield model LV viscometerhoused in a nitrogen purged drybox (in such a manner that the atmosphereis substantially free of moisture and oxygen, i.e. less than severalppmv of each). Supported Component A slurries are made up in a nitrogenpurged drybox, and rolled in their closed glass containers untilimmediately before the viscosity measurements are made, in order toensure that they are fully suspended at the start of the trial.Temperature of the viscometer is controlled via an external temperaturebath circulating heat transfer fluid into the viscometer. The spindle isa SC4-34 spindle Rheocalc V1.1 software, copyright 1995, BrookfieldEngineering Laboratories, purchased with the viscometer is preferablyused.

In one embodiment the composition formed by combining supportedComponent A with Component B has a viscosity of about 130 to about 2000cP at 20° C., more preferably about 150 to about 1000 cP at 20° C., morepreferably about 180 to about 1500 cP at 20° C. even more preferablyabout 200 to about 600 cP at 20° C.

Bulky Ligand Metallocene Catalyst Compounds

In the process of this invention useful catalyst compounds include thetraditional bulky ligand metallocene catalyst compounds include half andfull sandwich compounds having one or more bulky ligands bonded to atleast one metal atom. Typical bulky ligand metallocene compounds aregenerally described as containing one or more bulky ligand(s) and one ormore leaving group(s) bonded to at least one metal atom. In onepreferred embodiment, at least one bulky ligands is η-bonded to themetal atom, most preferably η⁵-bonded to the metal atom.

The bulky ligands are generally represented by one or more open,acyclic, or fused ring(s) or ring system(s) or a combination thereof.These bulky ligands, preferably the ring(s) or ring system(s) aretypically composed of atoms selected from Groups 13 to 16 atoms of thePeriodic Table of Elements, preferably the atoms are selected from thegroup consisting of carbon, nitrogen, oxygen, silicon, sulfur,phosphorous, germanium, boron and aluminum or a combination thereof.Most preferably the ring(s) or ring system(s) are composed of carbonatoms such as but not limited to those cyclopentadienyl ligands orcyclopentadienyl ligand structures or other similar functioning ligandstructure such as a pentadiene, a cyclooctatetraendiyl or an imideligand. The metal atom is preferably selected from Groups 3 through 15and the lanthanide or actinide series of the Periodic Table of Elements.Preferably the metal is a transition metal from Groups 4 through 12,more preferably Groups 4, 5 and 6, and most preferably the transitionmetal is from Group 4.

In one embodiment, the bulky ligand metallocene catalyst compounds ofthe invention are represented by the formula:L^(A)L^(B)MQ_(n) (I)where M is a metal atom from the Periodic Table of the Elements and maybe a Group 3 to 12 metal or from the lanthanide or actinide series ofthe Periodic Table of Elements, preferably M is a Group 4, 5 or 6transition metal, more preferably M is a Group 4 transition metal, evenmore preferably M is zirconium, hafnium or titanium. The bulky ligands,L^(A) and L^(B), are open, acyclic or fused ring(s) or ring system(s)and are any ancillary ligand system, including unsubstituted orsubstituted, cyclopentadienyl ligands or cyclopentadienyl ligands,heteroatom substituted and/or heteroatom containing cyclopentadienylligands. Non-limiting examples of bulky ligands include cyclopentadienylligands, cyclopentaphenanthreneyl ligands, indenyl ligands benzindenylligands, fluorenyl ligands, octahydrofluorenyl ligands,cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenylligands, azulene ligands, pentalene ligands, phosphoyl ligands,phosphinimine (WO 99/40125 and WO 00/05236), aminomethylphosphineligands (U.S. Pat. No. 6,034,240 and WO 99/46271), pyrrolyl ligands,pyrozolyl ligands, carbazolyl ligands, borabenzene ligands,B-diketiminate ligands (U.S. Pat. No. 6,034,258), fullerenes (U.S. Pat.No. 6,002,035) and the like, including hydrogenated versions thereof,for example tetrahydroindenyl ligands. In one embodiment, L^(A) andL^(B) may be any other ligand structure capable of η-bonding to M,preferably η³-bonding to M and most preferably η⁵-bonding. In yetanother embodiment, the atomic molecular weight (MW) of L^(A) or L^(B)exceeds 60 a.m.u., preferably greater than 65 a.m.u. In anotherembodiment, L^(A) and L^(B) may comprise one or more heteroatoms, forexample, nitrogen, silicon, boron, germanium, sulfur and phosphorous, incombination with carbon atoms to form an open, acyclic, or preferably afused, ring or ring system, for example, a hetero-cyclopentadienylancillary ligand. Other L^(A) and L^(B) bulky ligands include but arenot limited to bulky amides, phosphides, alkoxides, aryloxides, imides,carbolides, borollides, porphyrins, phthalocyanines, corrins and otherpolyazomacrocycles. Independently, each L^(A) and L^(B) may be the sameor different type of bulky ligand that is bonded to M. In one embodimentof formula (I) only one of either L^(A) or L^(B) is present.

Independently, each L^(A) and L^(B) may be unsubstituted or substitutedwith a combination of substituent groups R. Non-limiting examples ofsubstituent groups R include one or more from the group selected fromhydrogen, or linear, branched alkyl radicals, or alkenyl radicals,alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals,aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals,dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonylradicals, carbomoyl radicals, alkyl- or dialkyl-carbamoyl radicals,acyloxy radicals, acylamino radicals, aroylamino radicals, straight,branched or cyclic, alkylene radicals, or combination thereof. In apreferred embodiment, substituent groups R have up to 50 non-hydrogenatoms, preferably from 1 to 30 carbon, that can also be substituted withhalogens or heteroatoms or the like. Non-limiting examples of alkylsubstituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl,cyclopentyl, cyclohexyl, benzyl or plenyl groups and the like, includingall their isomers, for example tertiary butyl, isopropyl, and the like.Other hydrocarbyl radicals include fluoromethyl, fluroethyl,difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbylsubstituted organometalloid radicals including trimethylsilyl,trimethylgermyl, methyldiethylsilyl and the like; andhalocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)silyl, methyl-bis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstitiuted boronradicals including dimethylboron for example; and disubstitutedpnictogen radicals including dimethylamine, dimethylphosphine,diphenylamine, methylphenylphosphine, chalcogen radicals includingmethoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.Non-hydrogen substituents R include the atoms carbon, silicon, boron,aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and thelike, including olefins such as but not limited to olefinicallyunsaturated substituents including vinyl-terminated ligands, for examplebut-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two Rgroups, preferably two adjacent R groups, are joined to form a ringstructure having from 3 to 30 atoms selected from carbon, nitrogen,oxygen, phosphorous, silicon, germanium, aluminum, boron or acombination thereof. Also, a substituent group R group such as 1-butanylmay form a carbon sigma bond to the metal M.

Other ligands may be bonded to the metal M, such as at least one leavinggroup Q. For the purposes of this patent specification and appendedclaims the term “leaving group” is any ligand that can be abstractedfrom a bulky ligand metallocene catalyst compound to form a bulky ligandmetallocene catalyst cation capable of polymerizing one or moreolefin(s). In one embodiment, Q is a monoanionic labile ligand having asigma-bond to M. Depending on the oxidation state of the metal, thevalue for n is 0, 1 or 2 such that formula (I) above represents aneutral bulky ligand metallocene catalyst compound.

Non-limiting examples of Q ligands include weak bases such as amines,phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals havingfrom 1 to 20 carbon atoms, hydrides or halogens and the like or acombination thereof In another embodiment, two or more Q's form a partof a fused ring or ring system. Other examples of Q ligands includethose substituents for R as described above and including cyclobutyl,cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene,pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy,bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and thelike. In one embodiment, the bulky ligand metallocene catalyst compoundsof the invention include those of formula (I) where L^(A) and L^(B) arebridged to each other by at least one bridging group, A, such that theformula is represented byL^(A)AL^(B)MQ_(n)   (II)

These bridged compounds represented by formula (II) are known asbridged, bulky ligand metallocene catalyst compounds. L^(A), L^(B), M, Qand n are as defined above. Non-limiting examples of bridging group Ainclude bridging groups containing at least one Group 13 to 16 atom,often referred to as a divalent moiety such as but not limited to atleast one of a carbon, oxygen, nitrogen, sulfur, silicon, aluminum,boron, germanium and tin atom or a combination thereof. Preferablybridging group A contains a carbon, silicon or germanium atom, mostpreferably A contains at least one silicon atom or at least one carbonatom. The bridging group A may also contain substituent groups R asdefined above including halogens and iron. Non-limiting examples ofbridging group A may be represented by R′₂C, R′₂Si, R′₂Si R′₂Si, R′₂Ge,R′P, where R′ is independently, a radical group which is hydride,hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, hydrocarbyl-substituted organometalloid,halocarbyl-substituted organometalloid, disubstituted boron,disubstituted pnictogen, substituted chalcogen, or halogen or two ormore R′ may be joined to form a ring or ring system. In one embodiment,the bridged, bulky ligand metallocene catalyst compounds of formula (II)have two or more bridging groups A (EP 664 301 B1) or the bridge isheteroatomic (U.S. Pat. No. 5,986,025).

In one embodiment, the bulky ligand metallocene catalyst compounds arethose where the R substituents on the bulky ligands L^(A) and L^(B) offormulas (I) and (II) are substituted with the same or different numberof substituents on each of the bulky ligands. In another embodiment, thebulky ligands L^(A) and L^(B) of formulas (I) and (II) are differentfrom each other.

Other bulky ligand metallocene catalyst compounds and catalyst systemsuseful in the invention may include those described in U.S. Pat. Nos.5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022, 5,276,208,5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401, 5,723,398,5,753,578, 5,854,363, 5,856,547 5,858,903, 5,859,158, 5,900,517,5,939,503, 5,962,718, 5,965,078, 5,965,756, 5,965,757, 5,977,270,5,977,392, 5,986,024, 5,986,025, 5,986,029, 5,990,033 and 5,990,331 andPCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO 98/11144, WO98/41530, WO 98/41529, WO 98/46650, WO 99/02540, WO 99/14221 and WO98/50392 and European publications EP-A-0 578 838,-EP-A-0 638 595,EP-B-0 513 380, EP-Al-0 816 372, EP-A2-0 839 834, EP-B1-0 632 819,EP-B1-0 739 361, EP-B1-0 748 821 and EP-B1-0 757 996, all of which areherein fully incorporated by reference.

In one embodiment, bulky ligand metallocene catalyst compounds useful inthe invention include bridged heteroatom, mono-bulky ligand metallocenecompounds. These types of catalysts and catalyst systems are describedin, for example, PCT publication WO 92/00333, WO 94/07928, WO 91/04257,WO 94/03506, W096/00244, WO 97/15602 and WO 99/20637 and U.S. Pat. Nos.5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405 andEuropean publication EP-A-0 420 436, all of which are herein fullyincorporated by reference.

In this embodiment, the bulky ligand metallocene catalyst compound isrepresented by the formula:L^(C)AJMQ_(n)   (III)where M is a Group 3 to 16 metal atom or a metal selected from the Groupof actinides and lanthanides of the Periodic Table of Elements,preferably M is a Group 4 to 12 transition metal, and more preferably Mis a Group 4, 5 or 6 transition metal, and most preferably M is a Group4 transition metal in any oxidation state, especially titanium; L^(C) isa substituted or unsubstituted bulky ligand bonded to M; J is bonded toM; A is bonded to L^(C) and J; J is a-heteroatom ancillary ligand; and Ais a bridging group; Q is a univalent anionic ligand; and n is theinteger 0,1 or 2. In formula (III) above, L^(C), A and J form a fusedring system. In an embodiment, L^(C) of formula (III) is as definedabove for L^(A), A, M and Q of formula (III) are as defined above informula (I).

In formula (III) J is a heteroatom containing ligand in which J is anelement with a coordination number of three from Group 15 or an elementwith a coordination number of two from Group 16 of the Periodic Table ofElements. Preferably J contains a nitrogen, phosphorus, oxygen or sulfuratom with nitrogen being most preferred.

In another embodiment, the bulky ligand type metallocene catalystcompound is a complex of a metal, preferably a transition metal, a bulkyligand, preferably a substituted or unsubstituted pi-bonded ligand, andone or more heteroallyl moieties, such as those described in U.S. Pat.Nos. 5,527,752 and 5,747,406 and EP-B1-0 735 057, all of which areherein fully incorporated by reference.

In an embodiment, the bulky ligand metallocene catalyst compound isrepresented by the formula:L^(D)MQ₂(YZ)X_(n)   (IV)where M is a Group 3 to 16 metal, preferably a Group 4 to 12 transitionmetal, and most preferably a Group 4, 5 or 6 transition metal; L^(D) isa bulky ligand that is bonded to M; each Q is independently bonded to Mand Q₂(YZ) forms a unicharged polydentate ligand; A or Q is a univalentanionic ligand also bonded to M; X is a univalent anionic group when nis 2 or X is a divalent anionic group when n is 1; n is 1 or 2.

In formula (IV), L and M are as defined above for formula (I). Q is asdefined above for formula (I), preferably Q is selected from the groupconsisting of —O—, —NR—, —CR₂— and —S—; Y is either C or S; Z isselected from the group consisting of —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂,—H, and substituted or unsubstituted aryl groups, with the proviso thatwhen Q is —NR— then Z is selected from one of the group consisting of—OR, —NR₂, —SR, —SiR₃, —PR₂ and —H; R is selected from a groupcontaining carbon, silicon, nitrogen, oxygen, and/or phosphorus,preferably where R is a hydrocarbon group containing from 1 to 20 carbonatoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is aninteger from 1 ID 4, preferably 1 or 2; X is a univalent anionic groupwhen n is 2 or X is a divalent anionic group when n is 1; preferably Xis a carbamate, carboxylate, or other heteroallyl moiety described bythe Q, Y and Z combination.

In another embodiment of the invention, the metallocene catalystcompounds are heterocyclic ligand complexes where the bulky ligands, thering(s) or ring system(s), include one or more heteroatoms or acombination thereof. Non-limiting examples of heteroatoms include aGroup 13 to 16 element, preferably nitrogen, boron, sulfur, oxygen,aluminum, silicon, phosphorous and tin. Examples of these metallocenecatalyst compounds are described in WO 96/33202, WO 96/34021, WO97/17379, WO 98/22486 and WO 99/40095 (dicarbamoyl metal complexes) andEP-A1-0 874 005 and U.S. Pat. No. 5,637,660, 5,539,124, 5,554,775,5,756,611, 5,233,049, 5,744,417, and 5,856,258 all of which are hereinincorporated by reference.

In another embodiment, new metallocene catalyst compounds are thosecomplexes known as transition metal catalysts based on bidentate ligandscontaining pyridine or quinoline moieties, such as those described inU.S. application Ser. No. 09/103,620 filed Jun. 23, 1998, which isherein incorporated by reference. In another embodiment, the bulkyligand metallocene catalyst compounds are those described in PCTpublications WO 99/01481 and WO 98/42664, which are fully incorporatedherein by reference.

In one embodiment, these new metallocene catalyst compound isrepresented by the formula:((Z)XA_(t)(YJ))_(q)MQ_(n)   (V)where M is a metal selected from Group 3 to 13 or lanthanide andactinide series of the Periodic Table of Elements; Q is bonded to M andeach Q is a monovalent, bivalent, or trivalent anion; X and Y are bondedto M; one or more of X and Y are heteroatoms, preferably both X and Yare heteroatoms; Y is contained in a heterocyclic ring J, where Jcomprises from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbonatoms; Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms,preferably 1 to 50 carbon atoms, preferably Z is a cyclic groupcontaining 3 to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1;when t is 1, A is a bridging group joined to at least one of X,Y or J,preferably X and J; q is 1 or 2; n is an integer from 1 to 4 dependingon the oxidation state of M. In one embodiment, where X is oxygen orsulfur then Z is optional. In another embodiment, where X is nitrogen orphosphorous then Z is present. In an embodiment, Z is preferably an arylgroup, more preferably a substituted aryl group.

It is within the scope of this invention, in one embodiment, that thenew metallocene catalyst compounds include complexes of Ni²⁺ and Pd²⁺described in the articles Johnson, et al., “New Pd(II)- and Ni(II)-BasedCatalysts for Polymerization of Ethylene and a-Olefins”, J. Am. Chem.Soc. 1995, 117, 6414-6415 and Johnson, et al., “Copolymerization ofEthylene and Propylene with Functionalized Vinyl Monomers byPalladium(II) Catalysts”, J. Am. Chem. Soc., 1996, 118, 267-268, and WO96/23010 published Aug. 1, 1996, WO 99/02472, U.S. Pat. Nos. 5,852,145,5,866,663 and 5,880,241, which are all herein fully incorporated byreference. These complexes can be either dialkyl ether adducts, oralkylated reaction products of the described dihalide complexes that canbe activated to a cationic state by the activators of this inventiondescribed below. Other new metallocene catalysts include those nickelcomplexes described in WO 99/50313, which is incorporated herein byreference.

Also included as metallocene catalyst are those diimine based ligands ofGroup 8 to 10 metal compounds disclosed in PCT publications WO 96/23010and WO 97/48735 and Gibson, et. al., Chem. Comm., pp. 849-850 (1998),all of which are herein incorporated by reference. Group 6 bulky ligandmetallocene catalyst systems are described in U.S. Pat. No. 5,942,462,which is incorporated herein by reference.

Other metallocene catalysts are those Group 5 and 6 metal imidocomplexes described in EP-A2-0 816 384 and U.S. Pat. No. 5,851,945,which is incorporated herein by reference. In addition, metallocenecatalysts include bridged bis(arylamido) Group 4 compounds described byD. H. McConville, et al., in Organometallics 1195, 14, 5478-5480, whichis herein incorporated by reference. In addition, bridged bis(amido)catalyst compounds are described in WO 96/27439, which is hereinincorporated by reference. Other metallocene catalysts are described asbis(hydroxy aromatic nitrogen ligands) in U.S. Patent No. 5,852,146,which is incorporated herein by reference. Other metallocene catalystscontaining one or more Group 15 atoms include those described in WO98/46651, which is herein incorporated herein by reference. Still othermetallocene catalysts include those multinuclear metallocene catalystsas described in WO 99/20665 and U.S. Pat. No. 6,010,794, and transitionmetal metaaracyle structures described in EP 0 969 101 A2, which areherein incorporated herein by reference. Other metallocene catalystsinclude those described in EP 0 950 667 Al, double cross-linkedmetallocene catalysts (EP 0 970 074 Al), tethered metallocenes (EP 970963 A2) and those sulfonyl catalysts described in U.S. Pat. No.6,008,394, which are incorporated herein by reference.

It is also contemplated that in one embodiment, the bulky ligandmetallocene catalysts of the invention described above include theirstructural or optical or enantiomeric isomers (meso and racemic isomers,for example see U.S. Pat. No. 5,852,143, incorporated herein byreference) and mixtures thereof.

Illustrative but non-limiting examples of preferred bulky ligandmetallocene catalyst compounds include:

-   bis(cyclopentadienyl)titanium dimethyl,-   bis(cyclopentadienyl)titanium diphenyl,-   bis(cyclopentadienyl)zirconium dimethyl,-   bis(cyclopentadienyl)zirconium diphenyl,-   bis(cyclopentadienyl)haffium methyl and diphenyl,-   bis(cyclopentadienyl)titanium di-neopentyl,-   bis(cyclopentadienyl)zirconium di-neopentyl,-   bis(cyclopentadienyl)titanium dibenzyl,-   bis(cyclopentadienyl)zirconium dibenzyl,-   bis(cyclopentadienyl)vanadium dimethyl,-   bis(cyclopentadienyl)titanium methyl chloride,-   bis(cyclopentadienyl)titanium ethyl chloride,-   bis(cyclopentadienyl)titanium phenyl chloride,-   bis(cyclopentadienyl)zirconium methyl chloride,-   bis(cyclopentadienyl)zirconium ethyl chloride,-   bis(cyclopentadienyl)zirconium phenyl chloride,-   bis(cyclopentadienyl)titanium methyl bromide,-   cyclopentadienyl titanium trimethyl,-   cyclopentadienyl zirconium triphenyl,-   cyclopentadienyl zirconium trineopentyl,-   cyclopentadienyl zirconium trimethyl,-   cyclopentadienyl hafnium triphenyl,-   cyclopentadienyl hafnium trineopentyl,-   cyclopentadienyl hafnium trimethyl,-   pentamethylcyclopentadienyl titanium trichloride,-   pentaethylcyclopentadienyl titanium trichloride;-   bis(indenyl)titanium diphenyl or dichloride,-   bis(methylcyclopentadienyl)titanium diphenyl or dihalide,-   bis(1,2-dimethylcyclopentadienyl)titanium diphenyl or dichloride,-   bis(1,2-diethylcyclopentadienyl)titanium diphenyl or dichloride,-   bis(pentamethylcyclopentadienyl) titanium diphenyl or dichloride;-   dimethyl silyldicyclopentadienyl titanium diphenyl or dichloride,-   methyl phosphine dicyclopentadienyl titanium diphenyl or dichloride,-   methylenedicyclopentadienyl titanium diphenyl or dichloride,-   isopropyl(cyclopentadienyl)(fluorenyl)zirconium dichloride,-   isopropyl(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,-   diisopropylmethylene(cyclopentadienyl)(fluorenyl)zirconium    dichloride,-   diisobutylmethylene(cyclopentadienyl)(fluorenyl) zirconium    dichloride,-   ditertbutylmethylene(cyclopentadienyl)(fluorenyl)zirconium    dichloride,-   cyclohexylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride,-   diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)zirconium    dichloride,-   isopropyl(cyclopentadienyl)(fluorenyl)hafnium dichloride,-   diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,-   diisopropylmethylene(cyclopentadienyl)(fluorenyl)hafium dichloride,-   diisobutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,-   ditertbutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,-   cyclohexylidene(cyclopentadienyl)(fluorenyl)hafnium dichloride,-   diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)-hafnium    dichloride,-   isopropyl(cyclopentadienyl)(fluorenyl)titanium dichloride,-   diphenylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,-   diisopropylmethylene(cyclopentadienyl)(fluorenyl)titanium    dichloride,-   diisobutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,-   ditertbutylmethylene(cyclopentadienyl)(fluorenyl)titanium    dichloride,-   cyclohexylidene(cyclopentadienyl)(fluorenyl)titanium dichloride,-   diisopropylmethylene(2,5 dimethylcyclopentadienyl fluorenyl)titanium    dichloride,-   racemic-ethylene bis(1-indenyl)zirconium (W) dichloride,-   racemic-ethylene    bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,-   racemic-dimethylsilyl bis(1-indenyl) zirconium(IV)dichloride,-   racemic-dimethylsilyl    bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,-   racemic-1,1,2,2-tetramethylsilanylene    bis(1-indenyl)zirconium(IV)dichloride,-   racemic-1,1,2,2-tetramethylsilanylene    bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride,-   ethylidene(1-indenyl    tetramethylcyclopentadienyl)zirconium(IV)dichloride,-   racemic-dimethylsilyl    bis(2-methyl-4-t-butyl-1-cyclopentadienyl)zirconium(IV)dichloride,-   racemic-ethylene bis(1-indenyl)hafnium(IV)dichloride,    racemic-ethylene    bis(4,5,6,7-tetrahydro-1-indenyl)hafiium(IV)dichloride,-   racemic-dimethylsilyl bis(1-indenyl)hafaium(IV)dichloride,-   racemic-dimethylsilyl    bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV)dichloride,-   racemic-1,1,2,2-tetramethylsilanylene    bis(1-indenyl)hafnium(IV)dichloride,-   racemic-1,1,2,2-tetramethylsilanylene    bis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV), dichloride,-   ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)hafnium(IV)dichloride,-   racemic-ethylene bis(1-indenyl)titanium(IV)dichloride,    racemic-ethylene    bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride,-   racemic-dimethylsilyl bis(1-indenyl)titanium(IV)dichloride,-   racemic-dimethylsilyl    bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride,-   racemic-1,1,2,2-tetramethylsilanylene    bis(1-indenyl)titanium(IV)dichloride-   racemic-1,1,2,2-tetramethylsilanylene    bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride, and-   ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)titanium(IV)dichloride.

Particularly preferred metallocene catalysts are diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, racemic-dimethylsilylbis (2-methyl-1-indenyl) zirconium(IV)dichloride, racemic-dimethylsilylbis(2-methyl-4-(1-naphthyl-1-indenyl)zirconium(IV)dichloride, andracemic-dimethylsilyl bis(2-methyl-4-phenyl-1-indenyl)zirconium(IV)dichloride.

Phenoxide Catalyst Compounds

Preferred phenoxide catalysts include those represented by the formulae:

wherein R¹ is hydrogen or a C₄ to C₁₀₀ group, preferably a tertiaryalkyl group, preferably a C₄ to C₂₀ alkyl group, preferably a C₄ to C₂₀tertiary alkyl group, preferably a neutral C₄ to C₁₀₀ group and may ormay not also be bound to M, and at least one of R² to R⁵ is a groupcontaining a heteroatom, the rest of R² to R⁵ are independently hydrogenor a C₁ to C₁₀₀ group, preferably a C₄ to C₂₀ alkyl group (preferablybutyl, isobutyl, pentyl hexyl, heptyl, isohexyl, octyl, isooctyl, decyl,nonyl, dodecyl ) and any of R² to R⁵ also may or may not be bound to M,

-   -   O is oxygen, M is a group 3 to group 10 transition metal or        lanthanide metal, preferably a group 4 metal, preferably Ti, Zr        or Hf, n is the valence state of the metal M, preferably 2, 3,        4, or 5, Q is an alkyl, halogen, benzyl, amide, carboxylate,        carbamate, thiolate, hydride or alkoxide group, or a bond to an        R group containing a heteroatom which may be any of R¹ to R⁵ A        heteroatom containing group may be any heteroatom or a        heteroatom bound to carbon silica or another heteroatom.        Preferred heteroatoms include boron, aluminum, silicon,        nitrogen, phosphorus, arsenic, tin, lead, antimony, oxygen,        selenium, tellurium. Particularly preferred heteroatoms include        nitrogen, oxygen, phosphorus, and sulfur. Even more particularly        preferred heteroatoms include oxygen and nitrogen. The        heteroatom itself may be directly bound to the phenoxide ring or        it may be bound to another atom or atoms that are bound to the        phenoxide ring. The heteroatom containing group may contain one        or more of the same or different heteroatoms. Preferred        heteroatom groups include imines, amines, oxides, phosphines,        ethers, ketenes, oxoazolines heterocyclics, oxazolines,        thioethers, and the like. Particularly preferred heteroatom        groups include imines. Any two adjacent R groups may form a ring        structure, preferably a 5 or 6 membered ring. Likewise the R        groups may form multi-ring structures. In one embodiment any two        or more R groups do not form a 5 membered ring.

These phenoxide catalysts may be activated with activators includingalkyl aluminum compounds (such as diethylaluminum chloride), alumoxanes,modified alumoxanes, non-coordinating anions, non-coordinating group 13metal or metalliod anions, boranes, borates and the like preferredembodiment of which are described below.

See for example U.S. application Ser. No. 09/451,792, filed Dec. 1,1999, which is incorporated by reference herein, describing these typesof phenoxide catalyst compounds.

In a preferred embodiment the phenoxide catalyst compound comprises oneor more of:

-   bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;-   bis(N-ethyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;-   bis(N-iso-propyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;-   bis(N-t-butyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;-   bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;-   bis(N-hexyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;-   bis(N-phenyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;-   bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV)dibenzyl;-   bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dichloride;-   bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)dipivalate;-   bis(N-benzyl-3,5-di-t-butylsalicylimino)titanium(IV)dipivalate;-   bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)di(bis(dimethylamide));-   bis(N-iso-propyl-3,5-di-t-amylsalicylimino)zirconium(IV)dibenzyl;-   bis(N-iso-propyl-3,5-di-t-octylsalicylimino)zirconium(IV dibenzyl;-   bis(N-iso-propyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;-   bis(N-iso-propyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)titanium(IV)dibenzyl;-   bis(N-iso-propyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)hafnium(IV)dibenzyl;-   bis(N-iso-butyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)    dibenzyl;-   bis(N-iso-butyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)dichloride;-   bis(N-hexyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;-   bis(N-phenyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;-   bis(N-iso-propyl-3,5-di-(1′-methylcyclohexyl)lsalicylimino)zirconium(IV)dibenzyl;-   bis(N-benzyl-3-t-butylsalicylimino)zirconium(IV)dibenzyl;-   bis(N-benzyl-3-triphenylmethylsalicylimino)zirconium(IV)dibenzyl;-   bis(N-iso-propyl-3,5-di-trimethylsilylsalicylimino)zirconium(IV)dibenzyl;-   bis(N-iso-propyl-3-(phenyl)salicylimino)zirconium(IV)dibenzyl;-   bis(N-benzyl-3-(2′,6′-di-iso-propylphenyl)salicylimino)zirconium(IV)dibenzyl;-   bis(N-benzyl-3-(2′,6′-di-phenylphenyl)salicylimino)zirconium(IV)dibenzyl;-   bis(N-benzyl-3-t-butyl-5-methoxysalicylimino)zirconium(IV)dibenzyl;-   bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dibenzyl;-   bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dichloride;-   bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)di(bis(dimethylamide));-   bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′,1′-dimethylbenzyl)phenoxide)zirconium(IV)dibenzyl;-   bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)titanium(IV)dibenzyl;-   bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′,1′-dimethylbenzyl)phenoxide)titanium(IV)dibenzyl;-   bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′,1′-dimethylbenzyl)phenoxide)titanium(IV)dichloride;-   bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′,1′-dimethylbenzyl)phenoxide)haffium(IV)dibenzyl;-   (N-phenyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;-   (N-(2′,6′-di-iso-propylphenyl)-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;-   (N-(2′,6′-di-iso-propylphenyl)-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)titanium(IV)tribenzyl;    and-   (N-(2′,6′-di-iso-propylphenyl)-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)trichloride.    Activator and Activation Methods for the Metallocene Catalyst    Compounds

The above described catalyst compounds are typically activated invarious ways to yield catalyst systems having a vacant coordination sitethat will coordinate, insert, and polymerize olefin(s). For the purposesof this patent specification and appended claims, the term “activator”is defined to be any compound or component or method which can activateany of the catalyst compounds of the invention as described above.Non-limiting activators, for example may include a Lewis acid or anon-coordinating ionic activator or ionizing activator or any othercompound including Lewis bases, aluminum alkyls, conventionalcocatalysts and combinations thereof that can convert a neutraelmetallocene catalyst compound to a catalytically active bulky ligandmetallocene cation. It is within the scope of this invention to usealumoxane or modified alumoxane as an activator, and/or to also useionizing activators, neutral or ionic, such as tri (n-butyl) ammoniumtetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boronmetalloid precursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Pat.No. 5,942,459) or combination thereof, that would ionize the neutralmetallocene catalyst compound.

In one embodiment, an activation method using ionizing ionic compoundsnot containing an active proton but capable of producing both a catalystcation and a non-coordinating anion are also contemplated, and aredescribed in EP-A-0 426 637, EP-A-0 573 403 and U.S. Pat. No. 5,387,568,which are all herein incorporated by reference. An aluminum basedionizing activator is described in U.S. Pat. No. 5,602,269 and boron andaluminum based ionizing activators are described in WO 99/06414, whichare incorporated herein by reference, and are useful in this invention.

There are a variety of methods for preparing alumoxane and modifiedalumoxanes, non-limiting examples of which are described in U.S. Pat.No. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734,4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801,5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838,5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166, 5,856,256 and5,939,346 and European publications EP-A-0 561 476, EP-B1-0 279 586,EP-A-0 594-218 and EP-B1-0 586 665, and PCT publications WO 94/10180 andWO 99/15534, all of which are herein fully incorporated by reference. Apreferred alumoxane is a modified methyl alumoxane (MMAO) cocatalysttype 3A (commercially available from Akzo Chemicals, Inc. under thetrade name Modified Methylalumoxane type 3A, covered under patent numberU.S. Pat. No. 5,041,584).

Organoaluminum compounds as activators include trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum and the like.

Ionizing compounds may contain an active proton, or some other cationassociated with but not coordinated to or only loosely coordinated tothe remaining ion of the ionizing compound. Such compounds and the likeare described in European publications EP-A-0 570 982, EP-A-0 520 732,EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 and EP-A-0 277 004, andU.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025,5,384,299 and 5,502,124 and U.S. patent application Ser. No. 08/285,380,filed Aug. 3, 1994, all of which are herein fully incorporated byreference.

Other activators include those described in PCT publication WO 98/07515such as tris(2,2′,2″-nonafluorobiphenyl)fluoroaluminate, whichpublication is fully incorporated herein by reference. Combinations ofactivators are also contemplated by the invention, for example,alumoxanes and ionizing activators in combinations, see for example,EP-B1 0 573 120, PCT publications WO 94/07928 and WO 95/14044 and U.S.Pat. Nos. 5,153,157 and 5,453,410 all of which are herein fullyincorporated by reference. WO 98/09996 incorporated herein by referencedescribes activating metallocene catalyst compounds with perchlorates,periodates and iodates including their hydrates. WO 98/30602 and WO98/30603 incorporated by reference describe the use of lithium(2,2′-bisphenyl-ditrimethylsilicate)●4THF as an activator for ametallocene catalyst compound. WO 99/18135 incorporated herein byreference describes the use of organo-boron-aluminum activators. EP-B1-0781 299 describes using a silylium salt in combination with anon-coordinating compatible anion. Also, methods of activation such asusing radiation (see EP-B1-0 615 981 herein incorporated by reference),electro-chemical oxidation, and the like are also contemplated asactivating methods for the purposes of rendering the neutral metallocenecatalyst compound or precursor to a metallocene cation capable ofpolymerizing olefins. Other activators or methods for activating ametallocene catalyst compound are described in for example, U.S. Pat.Nos. 5,849,852, 5,859,653 and 5,869,723 and WO 98/32775, WO 99/42467(dioctadecylmethyl-ammonium-bis(tris(pentafluorophenyl)borane)benzimidazolide),which are herein incorporated by reference.

Illustrative, but not limiting examples of boron compounds which may beused as an activating cocatalyst in the preparation of the improvedcatalysts of this invention are tri-substituted ammonium salts such as:

-   trimethylammonium tetraphenylborate,-   triethylammonium tetraphenylborate,-   tripropylammonium tetraphenylborate,-   tri(n-butyl)ammonium tetraphenylborate,-   tri(t-butyl)ammonium tetraphenylborate,-   N,N-dimethylanilinium tetraphenylborate,-   N,N-diethylanilinium tetraphenylborate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,-   trimethylammonium tetrakis(pentafluorophenyl)borate,-   triethylammonium tetrakis(pentafluorophenyl)borate,-   tripropylammonium tetrakis(pentafluorophenyl)borate,-   tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,-   tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,-   N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,-   trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate,-   triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,-   dimethyl(t-butyl)ammonium    tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,    and-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate;-   di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,-   dicyclohexylammonium tetrakis(pentafluorophenyl)borate;-   triphenylphosphonium tetrakis(pentafluorophenyl)borate,-   tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, and-   tri(2,6-dimethylphenyl)phosphonium    tetrakis(pentafluorophenyl)borate.    Supports, Carriers and General Supporting Techniques

The above described catalyst compounds, activators and/or catalystsystems may be combined with one or more support materials or carriers.For example, in a preferred embodiment, the activator is contacted witha support to form a supported activator wherein the activator isdeposited on, contacted with, vaporized with, bonded to, or incorporatedwithin, adsorbed or absorbed in, or on, a support or carrier. In anotherpreferred embodiment the catalyst compound is contacted with a supportto form a supported catalyst compound wherein the catalyst compound isdeposited on, contacted with, vaporized with, bonded to, or incorporatedwithin, adsorbed or absorbed in, or on, a support or carrier. In anotherembodiment, the catalyst compound and the activator are combined andthereafter contacted with a support to form a supported catalyst systemwherein the system is deposited on, contacted with, vaporized with,bonded to, or incorporated within, adsorbed or absorbed in, or on, asupport or carrier.

Suitable support materials include inorganic or organic supportmaterials, preferably a porous support material. Non-limiting examplesof inorganic support materials include inorganic oxides and inorganicchlorides. Other carriers include resinous support materials such aspolystyrene, functionalized or crosslinked organic supports, such aspolystyrene divinyl benzene, polyolefins or polymeric compounds, or anyother organic or inorganic support material and the like, or mixturesthereof.

Preferred support materials include inorganic oxides that include thoseGroup 2, 3, 4, 5, 13 or 14 metal oxides. The preferred supports includesilica, fumed silica, alumina (WO 99/60033), silica-alumina and mixturesthereof. Other useful supports include magnesia, titania, zirconia,magnesium chloride (U.S. Pat. No. 5,965,477), montmorillonite (EP-B1 0511 665), phyllosilicate, zeolites, talc, clays (U.S. Pat. No.6,034,187) and the like. Also, combinations of these support materialsmay be used, for example, silica-chromium, silica-alumina,silica-titania and the like. Additional support materials may includethose porous acrylic polymers described in EP 0 767 184 B 1, which isincorporated herein by reference. Other support materials includenanocomposites as described in PCT WO 99/47598, aerogels as described inWO 99/48605, spherulites as described in U.S. Pat. No. 5,972,510 andpolymeric beads as described in WO 99/50311, which are all hereinincorporated by reference. A preferred support is fumed silica availableunder the trade name Cabosil™ TS-610, available from Cabot Corporation.Fumed silica is typically a silica with particles 7 to 30 nanometers insize that has been treated with dimethylsilyldichloride such that amajority of hydroxyl groups are capped.

It is preferred that the support material, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the support is in the range of fromabout 50 to about 500 m²/g, pore volume of from about 0.5 to about 3.5cc/g and average particle size of from about 10 to about 200 μm. Mostpreferably the surface area of the support is in the range from about100 to about 1000 m²/g, pore volume from about 0.8 to about 5.0 cc/g andaverage particle size is from about 5 to about 100 μm. The average poresize of the support material of the invention typically has pore size inthe range of from 10 to 1000 Å, preferably 50 to about 500 Å, and mostpreferably 75 to about 450 Å.

There are various methods known in the art for producing a supportedactivator or combining an activator with a support material. In anembodiment, the support material is chemically treated and/or dehydratedprior to combining with the catalyst compound, activator and/or catalystsystem.

In one embodiment, an alumoxane is contacted with a support material,preferably a porous support material, more preferably a inorganic oxide,and most preferably the support material is silica.

In an embodiment, the support material, having a various levels ofdehydration, preferably 200° C. to 600° C. dehydrated silica, that isthen contacted with an organoaluminum or alumoxane compound. Inspecifically the embodiment wherein an organoaluminum compound is used,the activator is formed in situ the support material as a result of thereaction of, for example, trimethylaluminum and water.

In yet another embodiment, a Lewis base-containing support substrateswill react with a Lewis acidic activator to form a support bonded Lewisacid compound. The Lewis base hydroxyl groups of silica are exemplary ofmetal/metalloid oxides where this method of bonding to a support occurs.This embodiment is described in U.S. patent application Ser. No.09/191,922, filed Nov. 13, 1998, which is herein incorporated byreference.

Other embodiments of supporting an activator are described in U.S. Pat.No. 5,427,991, where supported non-coordinating anions derived fromtrisperfluorophenyl boron are described; U.S. Pat. No. 5,643,847discusses the reaction of Group 13 Lewis acid compounds with metaloxides such as silica and illustrates the reaction oftrisperfluorophenyl boron with silanol groups (the hydroxyl groups ofsilicon) resulting in bound anions capable of protonating transitionmetal organometallic catalyst compounds to form catalytically activecations counter-balanced by the bound anions; immobilized Group IIIALewis acid catalysts suitable for carbocationic polymerizations aredescribed in U.S. Pat. No. 5,288,677; and James C. W. Chien, Jour. Poly.Sci.: Pt A: Poly. Chem, Vol.29, 1603-1607 (1991), describes the olefinpolymerization utility of methylalumoxane (MAO) reacted with silica(SiO₂) and metallocenes and describes a covalent bonding of the aluminumatom to the silica through an oxygen atom in the surface hydroxyl groupsof the silica.

In the preferred embodiment, the supported activator is formed bypreparing in an agitated, and temperature and pressure controlled vessela solution of the activator and a suitable solvent, then adding thesupport material at temperatures from 0C to 100° C., contacting thesupport with the activator solution for up to 24 hours, then using acombination of heat and pressure to remove the solvent to produce a freeflowing powder. Temperatures can range from 40 to 120° C. and pressuresfrom 5 psia to 20 psia (34.5 to 138 kPa). An inert gas sweep can also beused in assist in removing solvent. Alternate orders of addition, suchas slurrying the support material in an appropriate solvent then addingthe activator, can be used.

In an embodiment, the weight percent of the activator to the supportmaterial is in the range of from about 10 weight percent to about 70weight percent, preferably in the range of from 20 weight percent toabout 60 weight percent, more preferably in the range of from about 30weight percent to about 50 weight percent, and most preferably in therange of from 30 weight percent to about 40 weight percent.

Preferred slurries comprising supported activators and bulky ligandmetallocene catalyst compounds used in the process of this invention aretypically prepared by suspending the supported activator and/or catalystcompound in a liquid diluent. The liquid diluent is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane or anorganic composition such as mineral oil. The diluent employed should beliquid under the conditions of polymerization and relatively inert. Theconcentration of the components in the slurry is controlled such that adesired ratio of catalyst compound(s) to activator, and/or catalystcompound to catalyst compound is fed into the reactor. The componentsare generally fed into the polymerization reactor as a mineral oilslurry. Solids concentrations in oil are about 10-15 weight %,preferably 11-14 weight %.

Spray Drying

The metal compounds and/or the activators are may be combined with asupport material such as a particulate filler material and then spraydried, preferably to form a free flowing powder. Spray drying may be byany means known in the art. Please see EPA 0 668 295 B1, U.S. Pat. No.5,674,795 and U.S. Pat. No. 5,672,669 which particularly describe spraydrying of supported catalysts. In general one may spray dry thecatalysts by placing the catalyst compound and the optional activator insolution,( allowing the catalyst compound and activator to react, ifdesired), adding a filler material such as silica or Cabosil™ (asdescribed above), then forcing the solution at high pressures through anozzle. The solution may be sprayed onto a surface or sprayed such thatthe droplets dry in midair. The method generally employed is to dispersethe silica in toluene, stir in the activator solution, and then stir inthe catalyst compound solution. Typical slurry concentrations are about5-8 wt %. This formulation may sit as a slurry for as long as 30 minuteswith mild stirring or manual shaking to keep it as a suspension beforespray-drying. In one preferred embodiment, the makeup of the driedmaterial is about 40-50 wt % activator, (preferably alumoxane), 50-60SiO₂ and about˜2 wt % catalyst compound.

In another embodiment binders are added to the mix prior to spraydrying. These can be added as a means of improving the particlemorphology, i.e. narrowing the particle size distribution, lowerporosity of the particles and allowing for a reduced quantity ofalumoxane, which is acting as the ‘binder’.

The spray dried particles are generally fed into the polymerizationreactor as a mineral oil slurry. Solids concentrations in oil are about10-15 weight %, preferably 11 -14 weight %. In some embodiments, thespray dried particles are <˜10 micrometers in size from the lab-scaleBuchi spray-dryer, while the scaled up rotary atomizers can createparticles ˜25 micrometers, compared to conventional supported catalystswhich are ˜50 micrometers. In a preferred embodiment the support has anaverage particle size of 0.001 to 1 microns, preferably 0.001 to 0.1microns.

In a preferred embodiment, a slurry comprising a silica supported methylalumoxane and bis(2-methyl, 4-butyl cyclopentadienyl)zirconiumdichloride is combined on-line with a solution ofbis(N-iso-butyl-3-t-butylsalicyclimino)zirconium(IV)dibenzyl andintroduced into the reactor to produced ethylene homopolymers orcopolymers.

Catalyst System Addition Process

In a preferred embodiment a bulky ligand metallocene compound, a supportand an activator are combined to form a slurry. The slurry is typicallyprepared by suspending the support, the activator and catalyst compoundsin a liquid diluent. The liquid diluent is typically an alkane havingfrom 3 to 60 carbon atoms, preferably having from 5 to 20 carbon atoms,preferably a branched alkane, or an organic composition such as mineraloil or silicone oil. The diluent employed is preferably liquid under theconditions of polymerization and relatively inert.

The slurry is then preferably combined with a solution comprisingphenoxide catalyst compound. The solution is typically prepared bydissolving catalyst compound in a liquid solvent. The liquid solvent istypically an alkane, such as a C₅ to C₃₀ alkane, preferably a C₅ to C₁₀alkane. Cyclic alkanes such as toluene may also be used. A preferredsolvent is mineral oil. The solution employed should be liquid under theconditions of polymerization and relatively inert.

In a preferred embodiment, a slurry, preferably a mineral oil slurry,comprising at least one support, one bulky ligand metallocene compound,and at least one activator, preferably at least one supported activatoris mixed in a mixer (A). A solution is prepared by mixing a solvent andat least one phenoxide catalyst compound or activator in a mixer (C).The slurry is then combined in-line with the solution. A nucleatingagent, such as silica, alumina, fumed silica or any other particulatematter, may be added (B) to the slurry and or the solution in-line or inthe mixers (A) or (C). Similarly, additional activators or catalystcompounds (D) may be added in-line in powder or solution form to theslurry, the solution, or the combination of the slurry and the solution.The combination is then preferably mixed in-line (E) or in a mixer for aperiod of time, typically up to about 120 minutes, preferably about 1 toabout 60 minutes, more preferably about 5 to about 40 minutes, even morepreferably about 10 to about 30 minutes.

In another preferred embodiment, alkyls (F), such as an aluminum alkyl,an ethoxylated aluminum alkyl, an alumoxane, an anti-static agent or aborate activator, such as a C₁ to C₁₅ alkyl aluminum (for exampletri-isobutyl aluminum, trimethyl aluminum or the like), a C₁ to C₁₅ethoxylated alkyl aluminum or methyl alumoxane, ethyl alumoxane,isobutylalumoxne, modified alumoxane or the like are added to themixture of the slurry and the solution in line. The alkyls, antistaticagents, borate activators and/or alumoxanes may be added directly to themixture of the solution and the slurry or may be added via an alkane(such as isopentane, hexane, heptane, and or octane) carrier stream (G).Preferably, the alkyls, etc. are present at up to about 500 ppm, morepreferably at about 1 to about 300 ppm, more preferably at 10 to about300 ppm, more preferably at about 10 to about 100 ppm. Preferred carrierstreams include isopentane and or hexane. The alkane may be added (G) tothe mixture of the slurry and the solution, typically at a rate of about20 to about 60 lbs/hr (27 kg/hr). Likewise carrier gas, such asnitrogen, argon, ethane, propane and the like may be added in-line (H)to the mixture of the slurry and the solution. Typically the carrier gasmay be added at the rate of about 1 to about 100 lb/hr (0.445 kg/hr),preferably about 10 to about 50 lb/hr (5-23 kg/hr), more preferablyabout 1 to about 25 lb/hr (0.4-11 kg/hr).

Similarly, hexene (or other alpha-olefin or diolefin) may be addedin-line (J) to the mixture of the slurry and the solution. Theslurry/solution mixture is then preferably passed through an injectiontube (O) to the reactor (Q). The injection tube (O) may be supportedinside a larger support tube (S), such as a 1 inch (2.54 cm) tube. Insome embodiments, the injection tube may aerosolize the slurry/solutionmixture. In a preferred embodiment the injection tube has a diameter ofabout {fraction (1/16)} ths inch to about ½ inch (0.16 cm to 1.27 cm),preferably about {fraction (3/16)} ths inch to about ⅜ths inch (0.5 cmto 0.9 cm), more preferably ¼ inch to about ⅜ths inch (0.6 cm to 0.9cm).

Nucleating agents (K), such as fumed silica, can be added directly in tothe reactor. Recycle gas alone or in combination with ethylene or othermonomers can also be added back in to the reactor.

In another embodiment a plenum may be used in this invention. A plenumis a device used to create a particle lean zone in a fluidized bedgas-phase reactor, as described in detail in U.S. Pat. No. 5,693,727which is incorporated herein by reference. A plenum may have one, two,or more injection nozzles.

The catalyst injection tube passes into the reactor through a compressedchevron packing and extends into the fluid bed a distance of about 0.1inch to 10 feet (0.25 cm to 3.1 m), preferably about 1 inch to 6 ft (2.5cm to 1.8 m), and more preferably about 2 inches to 5 feet (5 cm to 1.5m). Typically, the depth of insertion depends on the diameter of thereactor and typically extends in about {fraction (1/20)}th to {fraction(2/4)}'s of the reactor diameter, preferably about {fraction (1/10)}thto ½ and more preferably about ⅕th to ⅓rd of the reactor diameter. Theend of the tube may be cut perpendicular to the axis to create a nozzlecone or point with an angle ranging from 0 to 90 degrees, preferablyranging from about 10 to 80 degrees. The lip of the hole can be taken toa new knife-edge. The tube can be positioned to reduce resin adhesion orcoated with an antifouling or antistatic compound. The tube can also becut diagonally at an angle simply from about 0 to 80 degrees off theaxial line of the tube, preferably about 0 to 60 degrees. The opening ofthe tube can be the same as the bore of the tube or expanded ordiminished to create a nozzle, with sufficient pressure drop andgeometry to provide a dispersed spray of a solution slurry and or powderinto the reactor, preferably into the fluid bed.

The injection tube can optionally be supported inside a structure withinthe fluid bed to provide structural integrity. This support tube istypically a heavy walled pipe with an internal diameter of from about ¼inch to about 5 inches (0.64 cm to 12.7 cm), preferably about ½ inch toabout 3 inches (1.3 cm to 7.6 cm), and more preferably about ¾ inch toabout 2 inches (1.9 cm to 5 cm). The support tube preferably extendsthrough the reactor wall to approximately the length of the injectiontube, allowing the injection tube to end just inside the end of thesupport tube or to extend past it up to about 10 inches (25.4 cm).Preferably, the injection tube extends about 0.5 to 5 inches (1.8 cm to12.7 cm) beyond the end of the support tube and more preferably about 1to 3 inches (2.5 cm to 7.6 cm). The end of the support tube in thereactor may be cut flat and perpendicular to the axis of the tube orpreferably, may be tapered at an angle ranging from about 10 to 80degrees. The end of the support tube may be polished or coated with ananti-static or anti-fouling material.

A purge flow of fluid (R) (typically fresh monomer, ethylene, hexaneisopentane, recycle gas, and the like) is preferably introduced fromoutside the reactor down the support tube to aid in dispersion of thesolution slurry or powder comprising catalyst compound and or activatorallowing the production of resin granular particles of good morphologywith decreased agglomeration and an APS (average particle size) in therange of about 0.005 to 0.10 inches (0.01 cm to 0.3 cm). The purge flowof fluid helps minimize fouling of the end of the catalyst injectiontube and support tubes. The fluid introduced to the support tube maycomprise hydrogen; olefins or diolefins, including but not limited to C₂to C₄₀ alpha olefins and C₂ to C₄₀ diolefins, ethylene, propylene,butene, hexene, octene, norbornene, pentene, hexadiene, pentadiene,isobutylene, octadiene, cyclopentadiene, comonomer being used in thepolymerization reaction, hydrogen; alkanes, such C₁ to C₄₀ alkanes,including but not limited to isopetane, hexane, ethane, propane, butane,and the like; mineral oil, cycle gas with or without condensed liquids;or any combination thereof. Preferably the support tube flow is freshethylene or propylene that may be heated or cycle gas that may be takenbefore or after passing through a heat exchanger. In addition, analkane, such as for instance isopentane or hexane, can be included inthe flow at the level ranging from about 0.001 wt %. to about 50% of theflow. The alkane can be dispersed in the flow and may exist as dispersedliquid droplets or be vaporized at the exit of the support tube. Thepresence of liquid may reduce fouling at the exit.

The flow rate of fluid in the support tube ranges from about 5 to 10,000pph and is somewhat dependent upon the reactor size. The linear velocityof the fluid in the support tube ranges from about 10 to 500 ft/sec (11to 549 km/hr), preferably about 20 to 300 ft/sec (22 to 329 km/hr) andmore preferably about 30 to 200 ft/sec (33 to 219 km/hr).

Alternatively, the exit of the support tube may be fashioned as anorifice or nozzle at the end to form a jet or dispersion of gas to aidin the distribution of the solution, slurry or powder comprisingcatalyst compound. In one embodiment, the internal diameter of thesupport tube is reduced gradually by about 3 to 80% at the end,preferably about 5 to 50% in a taper to create a nozzle to accelerate toand or disperse the fluid flow. The insertion of the injection tube isnot impacted by the internal taper of the support tube.

In an embodiment the contact temperature of Component A and Component Bis in the range of from 0° C. to about 80° C., preferably from about 0°C. to about 60° C., more preferably from about 10° C. to about 50° C.and most preferably from about 20° C. to about 40° C.

In one embodiment, the invention provides introducing the immobilizedcatalyst system in the presence of a mineral oil or a surface modifieror a combination thereof as described in PCT publication WO 96/11960 andU.S. Ser. No. 09/113,261 filed Jul. 10, 1998, which are herein fullyincorporated by reference. In a preferred embodiment a slurry of surfacemodifier, such as an aluminum stearate in mineral oil) is co-introduced(J) into the reactor with combination of the slurry and the solution. Inanother embodiment the surface modifier, such as aluminum stearate, wasadded into the slurry (A).

In another preferred embodiment the one or all of the catalysts arecombined with up to 6 weight % of a metal stearate, (preferably aaluminum stearate, more preferably aluminum distearate) or ananti-static agent based upon the weight of the catalyst, any support andthe stearate or anti-static agent, preferably 2 to 3 weight %. In oneembodiment, a solution or slurry of the metal stearate or anti-staticagent is fed into the reactor. The stearate or anti-static agent may becombined with the slurry (A) or the solution (C) or may be co-fed (R)with the combination of the slurry and the solution. In a preferredembodiment the catalyst compounds and or activators are combined withabout 0.5 to about 4 weight % of an antistat, such as a methoxylatedamine, such as Witco's Kemamine AS-990 from ICI Specialties inBloomington Delaware.

In another embodiment the catalyst system or the components thereof arecombined with benzil, xylitol, Irganox™ 565, sorbitol or the like andthen fed into the reactor. These agents may be dry tumbled with thecatalyst compounds and/or activators or may be fed into the reactor in asolution with or without the catalyst system or its components.Similarly these agents may be combined with the slurry (A) or thesolution (C) or may be co-fed (R) with the combination of the slurry andthe solution.

In another embodiment, the immobilized catalyst system or catalystsystem mixture or components thereof may be contacted with a carboxylatemetal salt as described in PCT publication WO 00/02930 and WO 00/2931,which are herein incorporated by reference.

In a preferred embodiment a mixer is present in the slurry tank (A) toagitate the slurry.

Polymerization Process

The catalyst systems prepared above are suitable for use in anyprepolymerization and/or polymerization process over a wide range oftemperatures and pressures. The temperatures may be in the range of from−60° C. to about 280° C., preferably from 50° C. to about 200° C., andthe pressures employed may be in the range from 1 atmosphere to about500 atmospheres or higher.

Polymerization processes include solution, gas phase, slurry phase and ahigh pressure process or a combination thereof. Particularly preferredis a gas phase or slurry phase polymerization of one or more olefins atleast one of which is ethylene or propylene.

In one embodiment, the process of this invention is directed toward asolution, high pressure, slurry or gas phase polymerization process ofone or more olefin monomers having from 2 to 30 carbon atoms, preferably2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms. Theinvention is particularly well suited to the polymerization of two ormore olefin monomers of ethylene, propylene, butene-1,pentene-1,4-methyl-pentene-1, hexene-1, octene-1 and decene-1.

Other monomers useful in the process of the invention includeethylenically unsaturated monomers, diolefins having 4 to 18 carbonatoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers andcyclic olefins. Non-limiting monomers useful in the invention mayinclude norbornene, norbornadiene, isobutylene, isoprene,vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidenenorbornene, dicyclopentadiene and cyclopentene.

In the most preferred embodiment of the process of the invention, acopolymer of ethylene is produced, where with ethylene, a comonomerhaving at least one alpha-olefin having from 4 to 15 carbon atoms,preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8carbon atoms, is polymerized in a gas phase process.

In another embodiment of the process of the invention, ethylene orpropylene is polymerized with at least two different comonomers,optionally one of which may be a diene, to form a terpolymer.

In one embodiment, the invention is directed to a polymerizationprocess, particularly a gas phase or slurry phase process, forpolymerizing propylene alone or with one or more other monomersincluding ethylene, and/or other olefins having from 4 to 12 carbonatoms. Polypropylene polymers may be produced using the particularlybridged bulky ligand metallocene catalysts as described in U.S. Pat.Nos. 5,296,434 and 5,278,264, both of which are herein incorporated byreference.

Typically in a gas phase polymerization process a continuous cycle isemployed where in one part of the cycle of a reactor system, a cyclinggas stream, otherwise known as a recycle stream or fluidizing medium, isheated in the reactor by the heat of polymerization. This heat isremoved from the recycle composition in another part of the cycle by acooling system external to the reactor. Generally, in a gas fluidizedbed process for producing polymers, a gaseous stream containing one ormore monomers is continuously cycled through a fluidized bed in thepresence of a catalyst under reactive conditions. The gaseous stream iswithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product is withdrawn from the reactor and freshmonomer is added to replace the polymerized monomer. (See for exampleU.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749,5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228, allof which are fully incorporated herein by reference.)

The reactor pressure in a gas phase process may vary from about 100 psig(690 kPa) to about 500 psig (3448 kPa), preferably in the range of fromabout 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferablyin the range of from about 250 psig (1724 kPa) to about 350 psig (2414kPa).

The reactor temperature in a gas phase process may vary from about 30°C. to about 120° C., preferably from about 60° C. to about 1 15° C.,more preferably in the range of from about 70° C. to 110° C., and mostpreferably in the range of from about 70° C. to about 95° C.

Other gas phase processes contemplated by the process of the inventioninclude series or multistage polymerization processes. Also gas phaseprocesses contemplated by the invention include those described in U.S.Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, and European publicationsEP-A-0 794 200 EP-B1-0 649 992, EP-A-0 802 202 and EP-B-634 421 all ofwhich are herein fully incorporated by reference.

In a preferred embodiment, the reactor utilized in the present inventionis capable and the process of the invention is producing greater than500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900Kg/hr) or higher of polymer, preferably greater than 1000 lbs/hr (455Kg/hr), more preferably greater than 10,000 lbs/hr (4540 Kg/hr), evenmore preferably greater than 25,000 lbs/hr (11,300 Kg/hr), still morepreferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even morepreferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferablygreater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr(45,500 Kg/hr).

A slurry polymerization process generally uses pressures in the range offrom about 1 to about 50 atmospheres and even greater and temperaturesin the range of 0° C. to about 120° C. In a slurry polymerization, asuspension of solid, particulate polymer is formed in a liquidpolymerization diluent medium to which ethylene and comonomers and oftenhydrogen along with catalyst are added. The suspension including diluentis intermittently or continuously removed from the reactor where thevolatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process must be operated abovethe reaction diluent critical temperature and pressure. Preferably, ahexane or an isobutane medium is employed.

A preferred polymerization technique of the invention is referred to asa particle form polymerization, or a slurry process where thetemperature is kept below the temperature at which the polymer goes intosolution. Such technique is well known in the art, and described in forinstance U.S. Pat. No. 3,248,179 which is fully incorporated herein byreference. Other slurry processes include those employing a loop reactorand those utilizing a plurality of stirred reactors in series, parallel,or combinations thereof. Non-limiting examples of slurry processesinclude continuous loop or stirred tank processes. Also, other examplesof slurry processes are described in U.S. Pat. No. 4,613,484 and5,986,021, which are herein fully incorporated by reference.

In an embodiment the reactor used in the slurry process of the inventionis capable of and the process of the invention is producing greater than2000 lbs of polymer per hour (907 Kg/hr), more preferably greater than5000 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr(4540 Kg/hr). In another embodiment the slurry reactor used in theprocess of the invention is producing greater than 15,000 lbs of polymerper hour (6804 Kg/hr), preferably greater than 25,000 lbs/hr (11,340Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

Examples of solution processes are described in U.S. Pat. Nos.4,271,060, 5,001,205, 5,236,998, 5,589,555 and 5,977,251 and PCT WO99/32525 and PCT WO 99/40130, which are fully incorporated herein byreference.

A preferred process of the invention is where the process, preferably aslurry or gas phase process is operated in the presence of a bulkyligand metallocene catalyst system of the invention and in the absenceof or essentially free of any scavengers, such as triethylaluminum,trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum anddiethyl aluminum chloride, dibutyl zinc and the like. This preferredprocess is described in PCT publication WO 96/08520 and U.S. Pat. Nos.5,712,352 and 5,763,543, which are herein fully incorporated byreference.

In one embodiment of the invention, olefin(s), preferably C₂ to C₃₀olefin(s) or alpha-olefin(s), preferably ethylene or propylene orcombinations thereof are prepolymerized in the presence of themetallocene catalyst systems of the invention described above prior tothe main polymerization. The prepolymerization can be carried outbatchwise or continuously in gas, solution or slurry phase including atelevated pressures. The prepolymerization can take place with any olefinmonomer or combination and/or in the presence of any molecular weightcontrolling agent such as hydrogen. For examples of prepolymerizationprocedures, see U.S. Pat. Nos. 4,748,221, 4,789,359, 4,923,833,4,921,825, 5,283,278 and 5,705,578 and European publication EP-B-0279863 and PCT Publication WO 97/44371 all of which are herein fullyincorporated by reference.

In one embodiment the polymerization catalyst is used in an unsupportedform, preferably in a liquid form such as described in U.S. Pat. Nos.5,317,036 and 5,693,727 and European publication EP-A-0 593 083, all ofwhich are herein incorporated by reference. The polymerization catalystin liquid form can be fed with a carboxylate metal salt and a flowimprover, as a solid or a liquid, to a reactor using the injectionmethods described in PCT publication WO 97/46599, which is fullyincorporated herein by reference.

Polymer Products

The polymers produced by the process of the invention can be used in awide variety of products and end-use applications. The polymers producedby the process of the invention include linear low density polyethylene,elastomers, plastomers, high density polyethylenes, medium densitypolyethylenes, low density polyethylenes, polypropylene andpolypropylene copolymers.

The polymers, typically ethylene based polymers, preferably have adensity in the range of from 0.86g/cc to 0.97 g/cc, preferably in therange of from 0.88 g/cc to 0.965 g/cc, more preferably in the range offrom 0.900 g/cc to 0.96 g/cc, even more preferably in the range of from0.905 g/cc to 0.95 g/cc, yet even more preferably in the range from0.910 g/cc to 0.940 g/cc, and most preferably in the range from about0.910 to about 0.925 g/cc. Density is measured in accordance withASTM-D-1238.

The polymers produced by the process of the invention preferably have amolecular weight distribution, i.e. the ratio of the weight averagemolecular weight to the number average molecular weight (M_(w)/M_(n)),of greater than 1.5 to about 15, particularly greater than 2 to about10, more preferably greater than about 2.2 to less than about 8, andmost preferably from 2.5 to 8.

Also, the polymers of the invention preferably have a narrow compositiondistribution as measured by Composition Distribution Breadth Index(CDBI). Further details of determining the CDBI of a copolymer are knownto those skilled in the art. See, for example, PCT Patent Application WO93/03093, published Feb. 18, 1993, which is fully incorporated herein byreference. Preferably the polymers produced herein have CDBI's generallyin the range of greater than 50% to 100%, preferably 99%, preferably inthe range of 55% to 85%, and more preferably 60% to 80%, even morepreferably greater than 60%, still even more preferably greater than65%.

In another embodiment, polymers produced herein have a CDBI less than50%, more preferably less than 40%, and most preferably less than 30%.

The polymers of the present invention preferably have a melt index (MI)or (12) as measured by ASTM-D-1238-E in the range from 0.01 dg/min to1000 dg/min, more preferably from about 0.05 dg/min to about 100 dg/min,even more preferably from about 0.1 dg/min to about 50 dg/min, and mostpreferably from about 0.1 dg/min to about 10 dg/min.

The polymers of the invention preferably have a melt index ratio(I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of from about 5 to less than40, more preferably from about 10 to less than 30, even more preferablyfrom about 15 to less than 25.

In another embodiment the process of this invention produces a polymerof ethylene having a density of 0.90 to 0.95 g/cc, preferably 0.905 to0.940g/cc, more preferably 0.910 to 0.930 g/cc, measured according toASTM D 1505.

In another embodiment the process of this invention produces a polymerof ethylene that when blown into a film of 15-35 microns thickness has a45° gloss of 60 or more, preferably 70 or more, preferably between 70and 100, measured according to ASTM D 2475, and/or a haze of 7% or less,preferably 6% or less, more preferably between 4 and 8%, measuredaccording to ASTM 1003-95, Condition A, and/or a dart impact of 600 g ormore, preferably 700 grams or more, preferably 750 grams or more,measured according to ASTM D 1709.

In a preferred embodiment the 15-35 μm thick films described above alsohave:

-   -   a) a TD tensile strength of 30 MPa or more, preferably 35 MPa or        more, preferably 40 MPa or more, measured according to ASTM D        882, and/or    -   b) an MD tensile strength of 30 MPa or more, preferably 35 MPa        or more, preferably 40 MPa or more, measured according to ASTM D        882, and/or    -   c) an MD modulus of 150 MPa or more, preferably 180 MPa or more,        preferably 200 MPa or more, measured according to ASTM D 412,        and/or    -   d) a TD modulus of 150 MPa or more, preferably 180 MPa or more,        preferably 200 MPa or more, measured according to ASTM D 412,        and/or

1e) an MD Elmendorf tear of 180 g/mil or more, preferably 200 g/mil ormore, preferably 250g/mil or more, measured according to ASTM D 1922,and/or

-   -   f) a TD Elmendorf tear of 300 g/mil or more, preferably 350        g/mil or more, preferably 400 g/mil or more, measured according        to ASTM D 1922.

In yet another embodiment, propylene based polymers are produced in theprocess of the invention. These polymers include atactic polypropylene,isotactic polypropylene, hemi-isotactic and syndiotactic polypropylene.Other propylene polymers include propylene block or impact copolymers.Propylene polymers of these types are well known in the art, see forexample U.S. Pat. Nos. 4,794,096, 3,248,455, 4,376,851, 5,036,034 and5,459,117, all of which are herein incorporated by reference.

The polymers of the invention may be blended and/or coextruded with anyother polymer. Non-limiting examples of other polymers include linearlow density polyethylenes produced via conventional Ziegler-Natta and/orbulky ligand metallocene catalysis, elastomers, plastomers, highpressure low density polyethylene, high density polyethylenes,polypropylenes and the like.

Polymers produced by the process of the invention and blends thereof areuseful in such forming operations as film, sheet, and fiber extrusionand co-extrusion as well as blow molding, injection molding and rotarymolding. Films include blown or cast films formed by coextrusion or bylamination useful as agricultural film, horticulture film, shrink film,cling film, stretch film, sealing films, oriented films, snackpackaging, heavy duty bags, grocery sacks, baked and frozen foodpackaging, medical packaging, industrial liners, membranes, etc. infood-contact and non-food contact applications. Fibers include meltspinning, solution spinning and melt blown fiber operations for use inwoven or non-woven form to make filters, diaper fabrics, medicalgarments, geotextiles, etc. Extruded articles include medical tubing,wire and cable coatings, pipe, geomembranes, and pond liners. Moldedarticles include single and multi-layered constructions in the form ofbottles, tanks, large hollow articles, rigid food containers and toys,etc.

EXAMPLES

In order to provide a better understanding of the present inventionincluding representative advantages thereof, the following examples areoffered.

Mn and Mw were measured by gel permeation chromatography on a waters150° C. GPC instrument equipped with differential refraction indexdetectors. The GPC columns were calibrated by running a series ofmolecular weight standards and the molecular weights were calculatedusing Mark Houwink coefficients for the polymer in question.

Melt Index (MI) I₂ and Flow Index (FI) I₂₁ were measured according toASTM D-1238, Condition E, at 190° C.

Melt Index Ratio (MIR) is the ratio of I₂, over I₂ as determined by ASTMD-1238.

I₂₁ was measured according to ASTM D-1238, Condition E, at 190° C.

Dart Impact Strength was measured according to ASTM D 1709.

Density was measured according to ASTM D 1505

MD and TD Elmendorf Tear were measured according to ASTM D 1922.

MD and TD tensile strength were measured according to ASTM D 882.

MD and TD elongation were measured according to ASTM D 412.

Haze was measured according to ASTM 1003-95, Condition A. 45° gloss wasmeasured according to ASTM D 2457. MD and TD Modulus were measuredaccording to ASTM D 412. BUR is blow up ratio. “PPH” is pounds per hour.“mPPH” is millipounds per hour. “ppmw” is parts per million by weight.“MD” is machine direction and “TD” is transverse direction. Linearlow-density polyethylene (LLDPE) polymers were produced usingbis(N-iso-butyl-3-t-butylsalicylimino)zirconium(IV)dibenzyl (Catalyst 1)and bis(1,3 methyl-n-butyl cyclopentadienyl)-zirconium dichloride(Catalyst 2).

Example 1

An ethylene hexene copolymer (Sample 1) was produced in a 14-inch (35.6cm) pilot plant scale gas phase fluidized bed reactor operating at 85°C. and 350 psig (2.4 MPa) total reactor pressure having a water cooledheat exchanger. Ethylene was fed to the reactor at a rate of about 46pounds per hour (21 kg/hr), hexene was fed to the reactor at a rate ofabout 4.9 pounds per hour (2.2 kg/hr) and hydrogen was fed to thereactor at a rate of 0.7 mPPH (0.0003 kg/hr). Ethylene was fed tomaintain 220 psi (1.5 MPa) ethylene partial pressure in the reactor.Hexene was continuously fed to maintain a 0.02 C6/C2 molar ratio.Hydrogen feed rate was controlled to maintain a 100-110 ppm hydrogen inthe cycle gas. The production rate was about 27 PPH (12.3 kg/hr). Thereactor was equipped with a plenum having about 2100 lb/hr (953 kg/hr)ofrecycle gas flow. (The plenum is a device used to create a particle leanzone in a fluidized bed gas-phase reactor. See U.S. Pat. No. 5,693,727.)A tapered catalyst injection nozzle having a 0.055 inch (0.14 cm) holesize was positioned in the plenum gas flow. A solution of 0.02 MolarCatalyst 1 in toluene was mixed with 0.1 lb/hr (0.05 kg/hr) hexene in a3/16 inch (0.1 cm) stainless steel tube. The Catalyst 1 and hexenemixture were mixed with cocatalyst (MMAO-3A, 1 wt % Aluminum in hexane)in a line for about 15 minutes. A 0.01 Molar Catalyst 2 in toluenesolution was added to the activated Catalyst 1 solution for about 5minutes before being sprayed into the reactor. The molar ratio ofCatalyst 2 to Catalyst 1 was 0.93. In addition to the solution, nitrogenwas added to the injection tube to help control particle size. Allmaterials were combine and were passed through the injection nozzle intothe fluidized bed. MMAO to catalyst ratio was controlled so that thefinal Al:Zr molar ratio was 500. The polymer residual zirconium of 0.53ppm was calculated based on a reactor mass balance.

Example 2

An ethylene hexene copolymer (Sample 2) was produced according to theprocedure in example 1 except that ethylene was fed to the reactor at arate of about 50 pounds per hour (22.7 kg/hr), hexene was fed to thereactor at a rate of about 6.1 pounds per hour (2.8 kg/hr) and hydrogenwas fed to the reactor at a rate of 0.8 mPPH (0.0004 kg/hr). Ethylenewas fed to maintain 220 psi ethylene partial pressure in the reactor.Hydrogen feed rate was controlled to maintain a 120 ppm hydrogen in thecycle gas. The production rate was about 34 PPH (15.4 kg/hr). The molarratio of Catalyst 2 to Catalyst 1 was 1.1. All materials were combinedand were passed through the injection nozzle into the fluidized bed.MMAO to catalyst ratio was controlled so that the final Al:Zr molarratio was 450. A polymer residual zirconium of 0.42 ppm was calculatedbased on a reactor mass balance.

Example 3

An ethylene hexene copolymer (Sample 3) was produced according to theprodecure in example 1 except that ethylene was fed to the reactor at arate of about 43 pounds per hour (19.5 kg/hr), hexene was fed to thereactor at a rate of about 4.8 pounds per hour (2.2 kg/hr) and hydrogenwas fed to the reactor at a rate of 0.5 milli pounds per hour (0.0002kg/hr). Hydrogen feed rate was controlled to maintain a 80 ppm hydrogenin the cycle gas. The production rate was about 25 PPH (11.3 kg/hr). Themolar ratio of Catalyst 2 to Catalyst 1 was 0.93. MMAO to catalyst ratiowas controlled so that the final Al:Zr molar ratio was 520. A polymerresidual zirconium of 0.5 ppm was calculated based on a reactor massbalance.

Example 4

Samples 1 and 2 were tumble-mixed with 1,000 ppm of Irganox 1076 and1,500 ppm of Irgafos and and then compounded on a 2.5 inch (6.4 cm)single screw (with double mixing head) Prodex extruder line. Thecompounded pelleted polymers were blown film extruded on the 3.5inch(8.9 cm) single-screw Gloucester film line which is equipped with adie of 6 inch(15.2 cm) diameter. The die gap varied between 60 mil(1524μm) and 90 mil(2286 μm) depending on samples. The die temperature wasset at between 400° F.(204° C.) and 410° F.(210° C.) depending on the MIof samples. The output rate was maintained at 150 lbs/hr(68 kg/hr) and1.0 mil(25.4 μm) film samples were produced with BUR of either at 2.5 or3.0. Reference polymers were selected among similar family of polymersthat are commercially available and whose flow properties match closelyto those of samples.

The two polymers (Samples 1 and 2) had melt indexes of 0.74 dg/min and0.98 dg/min, respectively, melt flow ratios of 18 and densities of 0.921g/cc and were blown into films. Exceed 350D60 (an ethylene polymeravailable from ExxonMobil Chemical Company in Baytown, Tex. having amelt index of 1.0, a melt flow ratio of 17 and a 0.917 g/cc) was used asa reference polymer. At the output rate of 150 b/hr(68 kg/hr) at dietemperature of 410° F.(210° C.), Sample 1 exhibited slightly higher headpressure while Sample 2 showed lower head pressure/motor load thanExceed 350D60. Bubble stability of Samples 1 and 2 were comparable tothat of reference polymer. One notable thing was the observation ofexcellent clarity from the blown bubble during film fabrication. Dartimpact strength of 1.0 mil(25.4 μm) of films produced at a 3.0 blow upratio of samples 1 and 2 were in the 610-630 g range in comparison with880g for Exceed 350D60. Other mechanical properties were comparable tothose of reference film sample. The 45 degree gloss and haze (%) offilms of Samples 1 and 2 were 61-75 and 5.2-6.9 compared to 41.5and 17for Exceed 350D60.

Example 5

Sample 3 was mixed with 600 ppm of Dynamar™ 9613 and compounded on theProdex line, was evaluated on the Gloucester film line as describedabove. The polymer had a melt index of 0.5 dg/min, a melt flow ratio of18.5 and a density of 0.920 g/cc. This time, Exceed 399L60 (an ethylenepolymer commercially available from ExxonMobil Chemical Company having amelt index of 0.75, a melt flow ratio of 17 and a density of 0.925 g/cc)was used as reference polymer. Due to lower MI, Sample 3 exhibitedhigher motor load and head pressure than Exceed 399L60. The bubblestability for sample 3 was as good as the reference polymer. 1.0 mil(25.4 μm) film sample produced at a 3.0 blow up ratio exhibited 800g ofdart impact strength in comparison with 180 g for Exceed 399L60.However, one should note that sample #3 has lower density (0.920 g/cc)than Exceed 399L60 (0.925 g/cc). A notable feature is again its filmclarity. Haze (%) was 3.9 and 45 degree gloss was 86 for Sample 3. Thedata are reported in Table 1. TABLE 1 Exceed 350D60 Sample 1 Sample 2Sample 3 Exceed 399L60 Melt Index (I₂)  1  0.74  0.98  0.49  0.75 dg/minFlow Index (I₂₁) dg/min  17  13.4  17.6  8.98  12.75 Melt Flow Ratio(I₂₁/I₂)  17  18.2  18  18.5  17 Density g/cc  0.917  0.921  0.921  0.92 0.925 Die set temp 210° C. 210° C. 210° C. 204° C. 204° C. Output Rate150 lb/hr 150 lb/hr 150 lb/hr 150 lb/hr 150 lb/hr (68 kg/hr) (68 kg/hr)(68 kg/hr) (68 kg/hr) (68 kg/hr) Head Pressure 4430 psi 4740 psi 3610psi 5440 psi 4790 psi 30.5 MPa 32.7 MPa 24.9 MPa 37.5 MPa 33.0 MPa Motorload (amp) 165 165 125 190 180 blow up ratio  3  3  3  3  3 Film gauge 1mil (25.4 μm) 1 mil (25.4 μm) 1 mil (25.4 μm) 1 mil (25.4 μm) 1 mil(25.4 μm) Dart Impact Strength (g) 880 610 630 800 180 MD TensileStrength 6500 psi 5900 psi 5600 psi 5600 psi 5450 psi 44.8 MPa 40.7 MPa38.6 MPa 38.6 MPa 37.6 MPa TD Tensile Strength   5600 psi   5800 psi  6300 psi   5760 psi   5700 psi 38.6 MPa 40.0 MPa 43.4 MPa 39.7 MPa39.3 MPa MD Elongation  580%  580%  570%  540%  650% TD Elongation  620% 630%  640%  610%  730% MD Modulus 24200 psi 35400 psi 30500 psi 29000psi 45400 psi 167 MPa 244 MPa 210 MPa 200 MPa 313 MPa TD Modulus 25800psi 35400 psi 36000 psi 36000 psi 47400 psi 178 MPa 244 MPa 248 MPa 248MPa 327 MPa MD Elmendorf Tear 284 g/mil 260 g/mil 300 g/mil 200 g/mil230 g/mil (11.2 g/μm) (10.2 g/μm) (11.8 g/μm) (7.9 g/μm) (90.1 g/μm) TDElmendorf Tear 366 g/mil 410 g/mil 440 g/mil 340 g/mil 350 g/mil (14.4g/μm) (16.1 g/μm) (17.3 g/μm) (13.4 g/μm) (13.8 g/μm) 45° Gloss  41.5 75.4   61  85.7  46.8 Haze   17%  5.2%  6.9%  3.9% 15.7%Exceed 350D60 and Exceed 399L60 are commercially available linear lowdensity polyethylene resins produced using a metallocene catalyst(ExxonMobil Chemical Company, Houston, Tex.).

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For example, it is contemplated that twoor more catalyst solutions of the invention can be used with two or moresupported activators. Also, it is contemplated that a conventionalZiegler-Natta catalyst on a silica and/or magnesium support can be usedwith a supported activator and a catalyst solution of the invention. Forthis reason, then, reference should be made solely to the appendedclaims for purposes of determining the true scope of the presentinvention.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures. As isapparent form the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly it is not intended thatthe invention be limited thereby.

1. A composition comprising a polymer of ethylene wherein the polymerhas a density of 0.910 to 0.930 g/cc, a melt index of 0.3-2.0 dg/min,and a 15-35 μm thick film of the polymer has a 45° gloss of 60 or more,a haze of 7% or less, a dart impact of 600 g or more.
 2. The compositionof claim 1 wherein the film also has a transverse direction tensilestrength of 30 MPa or more.
 3. The composition of claim 1 wherein thefilm also has a machine direction tensil strength of 30 MPa or more. 4.The composition of claim 1 wherein the film has a machine directionmodulus of 150 MPa or more.
 5. The composition of claim 1 wherein thefilm has a transverse direction modulus of 150 MPa or more.
 6. Thecomposition of claim 1 wherein the film has a machine directionElmendorf tear of 180 g/mil or more.
 7. The composition of claim 1wherein the film has a transverse direction Elmendorf tear of 300 g/milor more.
 8. The composition of claim 1 wherein the film also has: atransverse direction tensile strength of 30 MPa or more, a machinedirection tensil strength of 30 MPa or more, a machine direction modulusof 150 MPa or more, a transverse direction modulus of 150 MPa or more, amachine direction Elmendorf tear of 180 g/mil or more, and a transversedirection Elmendorf tear of 300 g/mil or more.